Uv-blocking borosilicate glass, the use of the same, and a fluorescent lamp

ABSTRACT

The invention relates to a borosilicate glass having the following composition (in wt. % based on oxide content): between 55 and 80 of SiO 2 ; between 8 and 25 of B 2 O 3 ; between 0.5 and 10 of Al 2 O 3 ; between 1 and 16 of Li 2 O+Na 2 O+K 2 O; between 0 and 6 of MgO+CaO+SrO+BaO; between 0 and 3 of ZnO; between 0 and 5 of ZrO 2 ; between 0 and 5 of Bi 2 O 3 ; and between 0 and 3 of MoO 3 ; the sum of the Bi 2 O 3  and MoO 3  amounting to between 0.01 and 5. The invention also relates to a fluorescent lamp, especially a miniature fluorescent lamp.

The invention relates to a UV-blocking borosilicate glass and to the use of the same. The invention also relates to a fluorescent lamp.

Fluorescent lamps, known as backlights, are used as background illumination for, for example, displays, for example of personal computers, laptops; palmtops, vehicle navigation systems.

Typical sizes of miniaturized lamps of this type are an external diameter of between 2 and 5 mm. Typical internal diameters are between 1.8 and 4.8 mm.

Whereas standard fluorescent tubes consist of a soft glass which has a very low solarization stability, glasses which are more solarization-stable are used for backlights, the basic structure of which corresponds to that of fluorescent tubes, in order to ensure long-term functionality.

On account of the structure of the backlights, the glasses used have to be suitable for vacuum-tight fusing to a metal or metal alloy used in lamp manufacture. For this purpose, they have to have a thermal expansion which is matched to the thermal expansion of the metal or metal alloy. For example, if tungsten is used, given the coefficient of thermal expansion α_(20/300) of W of 4.4×10⁻⁶/K, glasses with α_(20/300) of between 3.4×10⁻⁶/K and 4.3×10⁻⁶/K are particularly suitable. By way of example, if Kovar, an Fe—Co—Ni alloy, is used, glasses with α_(20/300) of between 4.3×10⁻⁶/K and 6.0×10⁻⁶/K are eminently suitable.

The glasses should Lend to have low working points V_(A), i.e. V_(A)<1200° C., to allow them to be worked at relatively low temperatures. The transformation temperature T_(g) should be matched to the melting characteristics of the metal or metal alloy to which it is to be fused. For example, in the case of fusing to Kovar, the transformation temperature should preferably be between 440° C. and 530° C. T_(g) of up to 580° C. is eminently suitable for fusing to tungsten.

The transmission profile is a significant property of glasses. In the visible region, the highest possible light transmission is required, in order to obtain a high light yield from the lamp, whereas in the UV region no transmission or only a low transmission is the aim; in order for the minimum possible amount of the harmful UV radiation to be allowed to pass through. The UV-blocking requirements depend on the uses of the glasses. For example, if they are used as lamp glasses for fluorescent lamps, in particular the Hg line at 253 nm should be blocked.

For example, for backlights, a high UV blocking≦253 nm is desirable in order to ensure that irradiated plastic parts, for example in laptops, do not become yellow and embrittled. This requirement is met by glasses having a UV transmission at λ≦254 nm of τ≦0.1%, measured on specimens which are 0.2 mm thick. For other uses, an UV transmission τ≦0.1% at λ≦240 nm is sufficient. In any event, the transition from the wavelength range which is not transmitted to the wavelength range which is transmitted should be as short as possible, i.e. the transmission curve should be as steep as possible in this region.

The minimum demand imposed on the transmission in the visible wavelength region is, at λ>400 nm and with a specimen thickness of 0.2 mm, a transmission of 90%. Therefore, the requirement is τ (>400 nm; 0.2 mm)≧90%.

A further important property of glasses for fluorescent lamps, in particular for backlights, is the resistance to solarization which is required in order to allow a long lamp service life to be achieved, i.e. a light yield which remains as constant as possible. In the present context, the term “solarization-stable” is to be understood as encompassing glasses which have a drop in transmission of at most 5% at 300 nm after 15 hours' HOK-4 irradiation, i.e. irradiation with an Hg high-pressure lamp with a main emission of 365 nm and an irradiation strength of 850 μW/cm² at 200 to 280 nm at a distance of 1 m on a glass specimen which is 0.2 mm thick.

The patent literature has already disclosed various documents which describe more or less UV-blocked glasses, in particular lamp glasses. However, these glasses have certain drawbacks, in particular a UV-blocking action which does not comply with the high demands imposed nowadays.

The borosilicate glass for discharge lamps which is described in JP 8-12369 A contains, for UV blocking purposes, a total of from 0.03 to 3% by weight of at least two of the four components V₂O₅, Fe₂O₃, TiO₂ and CeO₂. A high transmission and a high solarization resistance cannot be set using these components, in some cases in high individual proportions, and combinations thereof.

U.S. Pat. No. 5,747,399 describes a glass for miniaturized fluorescent lamps which is supposed to retain its solarization stability and its UV-impermeability by means of TiO₂ and/or PbO and/or Sb₂O₃. However, doping with TiO₂, in particular high levels of the latter, leads to discoloration of the class. PbO should also not be used, on account of the associated environmental problems.

Therefore, it is an object of the present invention to provide a glass having a high transmission in the visible region (>400 nm) and a high level of blocking in the UV region (≦240 nm), and also having a thermal expansion which is matched to the expansion of tungsten or Kovar.

The object is achieved by a borosilicate glass in accordance with the main claim.

A glass having the desired transmission properties comprises the base glass system (in % by weight, based on oxide): 55 to 80 SiO₂, 8 to 25 B₂O₃, 0.5 to 10 Al₂O₃, 1 to 16 Li₂O+Na₂O+K₂O, 0 to 6 MgO+CaO+SrO+BaO, 0 to 3 ZnO and 0 to 5 ZrO₂.

The presence of MoO₃ and/or Br₂O₃, specifically in a total amount of from 0.01 to 5% by weight, with from 0 to 3% of MoO₃ and from 0 to 5% of Bi₂O₃, is crucial to the invention.

The minimum level of MoO₃ and/or Bi₂O₃ is a requirement in order to achieve the high UV blocking. Higher levels of MoO₃ and/or Bi₂O₃ would lead to discoloration of the glass. A minimum total amount of 0.1% by weight is preferred, and a minimum total amount of 0.2% by weight is particularly preferred, as is a maximum total amount of 3% by weight. A minimum MoO₃ content of 0.4% by weight or a minimum Bi₂O₃ content of 1.0% by weight is particularly preferred. Bi₂O₃ also greatly improves the solarization stability of the glass. In particular in the particularly preferred embodiments, it is possible to achieve UV blocking up to 254 nm, i.e. a τ≦0.1% at τ≦254 nm with a specimen thickness of 0.2 mm. A minimum MoO₂ content of 0.6% by weight or a minimum Bi₂O₃ content of 0.3% by weight is very particularly preferred.

The glass preferably comprises the glass system (in % by weight, based on oxide): SiO₂ 55-79, B₂O₃ 10-25, Al₂O₃ 0.5-10, Li₂O+Na₂O+K₂O 1-16, MgO+CaO+SrO+BaO 0-6, ZnO 0-3, ZrO₂ 0-1; Bi₂O₃ 0-5, MoO₃ 0-3; with BiO₂+MoO₃ 0.1-5.

It is particularly preferred for the glass to comprise the following glass system: SiO₂ 55-79, B₂O₃ 8-12.5; Al₂O3 0.5-10; Li₂O+Na₂O+K₂O 1-16; MgO+CaO+SrO+BaO 0-6; ZnO 0-3; ZrO₂ 0-3; Bi₂O₃ 0-5; MoO₃ 0-3; with Bi₂O₃+MoO₃ 0.01-5.

It is preferable not to add ZrO₂, so that the glass is ZrO₂-free, apart from inevitable impurities resulting from raw materials or tank furnace corrosion.

Glasses from the abovementioned composition ranges containing from 70-80% by weight of SiO₂ have coefficients of thermal expansion α_(20/300) of between 3.4×10⁻⁶/K and 4.3×10⁻⁶/K and are therefore particularly suitable for fusing to tungsten.

Glasses from the composition range (in % by weight, based on oxide) SiO₂ 73-79, B₂O₃ 12.5-25; Al₂O₃ 0.5-10; Li₂O+Na₂C+K₂O 1-11; MgO+CaO+SrO+BaO 0-6; ZnO 0-3; ZrO₂ 0-5; Bi₂O₃ 0-5; MoO₃ 0-3; with Bi₂O₃+MoO₃ 0.01-5 are particularly preferred for fusing to tungsten.

Glasses from the abovementioned composition ranges containing from 55-75% by weight of SiO₂ have coefficients of thermal expansion of between 4.3×10⁻⁶/K and 6.0×10⁻⁶/K and are therefore particularly suitable for fusing to Kovar.

Glasses from the composition range (in % by weight, based on oxide) SiO₂ 55-73; B₂O₃ 15-25; Al₂O₃ 1-10; Li₂O+Na₂O+K₂O 4-16; MgO+CaO+SrO+BaO 0-6; ZnO 0-3; ZrO₂ 0-5; Bi₂O₃ 0-5; MoO₃ 0-3; with Bi₂O₃+MoO₃ 0.01-5 are particularly preferred for fusing to Kovar.

The glass may contain the usual quantities of standard refining agents, such as for example evaporation refining agents, such as Cl⁻ and F⁻, but also Redox refining agents, which are active on account of their polyvalent cations, e.g. SnO₂ and Sb₂O₃. It is preferable for the glass to contain 0-1% by weight of Sb₂O₃, 0-1% by weight of As₂O₃, 0-1% by weight of SnO₂, 0-1% by weight of CeO₂, 0-0.5% by weight of Cl, 0-1% by weight of F, 0-0.5 of sulfate, given as SO₃.

CeO₂ assists with the refining but may have an adverse effect on the solarization stability if it is present in excessive quantity.

Furthermore, the glass may contain 0-5% by weight of TiO₂, preferably 0-1% by weight of TiO₂, and 0-3% by weight of PbO. TiO₂ assists MoO₃ and Bi₂ O₃ by shifting the UV edge, i.e. the transition between absorption and transmission, into the longer-wave range. This makes it possible to achieve UV-blocking actions not only up to 240 nm, but even up to 254 nm and above, even with only the abovementioned low levels of MoO₃ and/or Bi₂O₃. The doping according to the invention, compared to the TiO₂ doping of the prior art, makes it possible to dispense altogether with TiO₂ or to add it in such small quantities that its disruptive discoloration plays no role.

The glass may contain up to 1% by weight of Fe₂O without this having any disadvantageous effect. Fe O also contributes to shifting the absorption edge into the longer-wave region.

The glass may also contain small proportions, which have no adverse effect on the glass system, of V₂O₅, Nb₂O₅ and WO₃.

The total quantity of Fe₂O₃, CeO₂, V₂O₅, Nb₂O₅, WO₃, TiO₂, PbO, As₂O₃, Sb₂O₃ should not exceed 5% by weight, since otherwise the glass is excessively discolored in the visible region.

EXEMPLARY EMBODIMENTS

Standard raw materials were used to produce the example glasses and the comparison glasses.

The well-homogenized batch was melted, refined and homogenized in the laboratory in a quartz glass crucible at 1600° C. Then, the glass was cast and cooled at 20 K/h.

The table shows thirteen examples of glasses according to the invention (A1 to A13) and two comparative examples (C1, C2) including their compositions (in % by weight, based on oxide) and their main properties.

The following properties are given in the table:

-   -   the coefficient of thermal expansion α_(20/300) [10⁻⁶/K]     -   the transformation temperature T_(g) [° C.]     -   the working point V_(A) [° C.]     -   the softening point E_(W) [° C.]

the highest wavelength at which τ is at most 0.1% (for a specimen thickness of 0.2 mm) to document the blocking in the UV region (“UV blocking”) TABLE Compositions (in % by weight, based on oxide) and important properties of glasses according to the invention (A) and of comparison glasses (C) C1 C2 A1 A2 A3 A4 A5 A6 A7 SiO₂ 68.45 67.65 72.6 78.0 72.0 68.0 59.0 69.0 68.25 B₂O₃ 19.0 19.0 14.5 10.8 16.0 12.0 16.0 8.0 19.0 Al₂O₃ 2.65 2.65 2.0 2.0 3.0 1.0 2.0 5.0 2.65 Na₂O 0.8 0.8 2.0 2.0 2.0 1.0 1.0 1.0 0.8 K₂O 7.7 7.7 — 1.0 1.0 3.0 3.0 3.0 7.7 MgO — — 0.5 1.0 1.0 4.0 4.0 4.0 — CaO — — 2.0 0.9 1.9 1.9 3.9 1.9 — SrO — — 1.6 1.0 1.0 1.0 1.0 1.0 — BaO — — — — — 5.0 5.0 2.0 — Li₂O 0.7 0.7 1.0 1.0 1.0 2.0 2.0 2.0 0.7 ZnO 0.6 0.6 2.4 1.0 1.0 1.05 2.0 2.0 0.6 As₂O₃ 0.1 0.1 0.1 — 0.1 — 0.1 0.1 0.1 Sb₂O₃ — — — 0.10 — — — — — Cl — — — — — 0.05 — — — TiO₂ — 0.8 — — — — 0.8 — — Bi₂O₃ — — 1.30 — 0.80 — 0.2 0.7 0.2 MoO₃ — — — 1.20 — 0.60 — 0.3 — α_(20/300) [10⁻⁶/K] 4.68 4.73 3.45 3.42 3.77 5.24 5.78 4.97 4.7 Tg [° C.] 485 491 505 515 502 455 449 487 485 V_(A) [° C.] 1055 1053 1078 1190 1062 872 729 999 1050 E_(w) [° C.] 720 715 761 791 751 626 588 690 720 UV-blocking [nm] <240 261 254 268 250 254 265 251 242 A8 A9 A10 A11 A12 A13 SiO₂ 67.95 66.45 67.65 67.95 67.45 67.85 B₂O₃ 19.0 19.0 19.0 19.0 19.0 19.0 Al₂O₃ 2.65 2.65 2.65 2.65 2.65 2.65 Na₂O 0.8 0.8 0.8 0.8 0.8 0.8 K₂O 7.7 7.7 7.7 7.7 7.7 7.7 MgO — — — — — — CaO — — — — — — SrO — — — — — — BaO — — — — — — Li₂O 0.7 0.7 0.7 0.7 0.65 0.65 ZnO 0.6 0.6 0.6 0.6 0.60 0.60 As₂O₃ 0.1 0.1 0.1 0.1 0.10 0.10 Sb₂O₃ — — — — — — Cl — — — — — — TiO₂ — — — — — — Bi₂O₃ — 2.0 0.8 — — 0.2 MoO₃ 0.5 — — 0.8 1.0 0.4 α_(20/300) [10⁻⁶/K] 4.72 4.81 4.8 4.8 4.86 4.73 Tg [° C.] 485 480 487 485 468 485 V_(A)[° C.] 1050 1040 1053 1050 1051 1050 E_(w) [° C.] 720 720 720 720 710 720 UV-blocking [nm] 248 259 248 255 262 251

Comparative Example C1 has a UV edge at too low a wavelength, i.e. it does not sufficiently block the UV region.

The TiO₂-containing Comparative Example C2 has a good UV-blocking action, as is also achieved by the doped glasses without the addition of TiO₂ in accordance with the invention.

Exemplary embodiments A1, A3, A7, A9 and A20 show glasses doped purely with Bi₂O₃. A2, A4, A8, A11 and A12 show glasses doped purely with MoO₃. A6 and A13 are examples of mixed doping with Bi₂O₃ and MoO₃. A5 reveals the boosting action of the optional component TiO₂ or, compared to C2, the improvement in the blocking achieved by the invention without it being necessary to increase the TiO₂ content.

The glasses according to the invention have a high resistance to solarization, expressed by Δ₁₅τ (300 nm; 0.2 mm) of <5%, a high transmission in the visible region, expressed by τ (>400 nm; 0.2 mm)≧90% and a good UV-blocking action, in particular expressed by τ (≦240 nm; 0.2 mm)≦0.1% or by the detail giving the highest wavelength at which τ is at most 0.1% (specimen thickness 0.2 mm). This wavelength is 240 nm or more.

In the preferred embodiments, the glasses have a UV transmission at λ≦254 nm of τ≦0.1%.

Furthermore, the glasses have a working point V; of <1200° C., so that they can be worked successfully.

The glasses have transformation temperatures T_(g) of between 440° C. and 580° C. They are therefore suitable for fusing to Kovar, for which purpose it is preferable to use the glasses with T_(g) of between 440° C. and 530° C., or to, tungsten, for which purpose it is preferable to use the glasses with a higher T_(g).

Furthermore, the glasses have a coefficient of thermal expansion α_(20/300) of between 3.4×10⁻⁶/K and 6.0×10⁻⁶/K. They are therefore sufficiently well matched to the thermal expansion of tungsten or Kovar, i.e. can be fused to one of these materials in a vacuum-tight manner.

With these properties and with τ≦0.1% at λ≦254 nm, the glasses are eminently suitable for the production of fluorescent lamps.

The glasses have a high resistance to crystallization. Consequently, the glasses are eminently suitable for tube drawing, in particular including for the drawing of tubes having the small diameters mentioned above. Therefore, the glasses for fluorescent lamps are also exceedingly well suited to the production of miniaturized fluorescent lamps, for example for the background illumination of displays, e.g. of personal computers, laptops, notebooks, palmtops, vehicle navigation systems, scanners, but also of mirrors and pictures.

The fluorescent lamps produced using the glasses according to the invention, in particular miniaturized fluorescent lamps, satisfy the demands imposed on such lamps. 

1. A borosilicate glass, having a composition (in % by weight, based on oxide) of SiO₂ 55-80 B₂O₃  8-25 Al₂O₃ 0.5-10  Li₂O + Na₂O + K₂O  1-16 MgO + CaO + SrO + BaO 0-6 ZnO 0-3 ZrO₂ 0-5 Bi₂O₃ 0-5 MoO₃ 0-3 with Bi₂O₃ + MoO₃ 0.01-5  


2. The borosilicate glass as claimed in claim 1, characterized by a composition (in % by weight, based on oxide) of SiO₂ 55-79 B₂O₃ 10-25 Al₂O₃ 0.5-10  Li₂O + Na₂O + K₂O  1-16 MgO + CaO + SrO + BaO 0-6 ZnO 0-3 ZrO₂ 0-1 Bi₂O₃ 0-5 MoO₃ 0-3 with Bi₂O₃ + MoO₃ 0.01-5  


3. The borosilicate glass as claimed in claim 1, characterized by a composition (in % by weight, based on oxide) of SiO₂ 73-79 B₂O₃ 12.5-25   Al₂O₃ 0.5-10  Li₂O + Na₂O + K₂O  1-11 MgO + CaO + SrO + BaO 0-6 ZnO 0-3 ZrO₂ 0-5 Bi₂O₃ 0-5 MoO₃ 0-3 with Bi₂O₃ + MoO₃ 0.01-5  


4. The borosilicate glass as claimed in claim 1, characterized by a composition (in % by weight, based on oxide) of SiO₂ 55-73 B₂O₃ 15-25 Al₂O₃  1-10 Li₂O + Na₂O + K₂O  4-16 MgO + CaO + SrO + BaO 0-6 ZnO 0-3 ZrO₂ 0-5 Bi₂O₃ 0-5 MoO₃ 0-3 with Bi₂O₃ + MoO₃ 0.01-5  


5. The borosilicate glass as claimed in claim 1, characterized by a composition (in % by weight, based on oxide) of SiO₂ 55-79 B₂O₃   8-12.5 Al₂O₃ 0.5-10  Li₂O + Na₂O + K₂O  1-16 MgO + CaO + SrO + BaO 0-6 ZnO 0-3 ZrO₂ 0-3 Bi₂O₃ 0-5 MoO₃ 0-3 with Bi₂O₃ + MoO₃ 0.01-5  


6. The borosilicate glass as claimed in at least one of claims 1 to 5, characterized in that the sum of Bi₂O₃ and MoO₃ is between 0.1% by weight and 5% by weight, preferably between 0.2% by weight and 3% by weight.
 7. The borosilicate glass as claimed in at least one of claims 1 to 6, characterized in that it additionally contains (in % by weight, based on oxide): Fe₂O₃ 0-1 CeO₂ 0-1 TiO₂ 0-5 PbO 0-3 As₂O₃ 0-1 Sb₂O₃ 0-1 with Fe₂O₃ + CeO₂ + TiO₂ + PbO + 0-5 As₂O₃ + Sb₂O₃ + V₂O₅ + Nb₂O₅ + WO₃ SnO₂ 0-1 F 0-1 Cl   0-0.5 SO₃   0-0.5


8. The borosilicate glass as claimed in at least one of claims 1 to 7, having a transformation temperature Tg of between 440° C. and 580° C., having a coefficient of thermal expansion α_(20/300) of between 3.4×10⁻⁶/K and 6.0×10⁻⁶/K, a transmission τ at λ≦240 nm of ≦0.1% (for a specimen thickness of 0.2 mm).
 9. The borosilicate glass as claimed in at least one of claims 1 to 7, having a transformation temperature Tg of between 440° C. and 580° C., having a coefficient of thermal expansion α_(20/300) of between 3.4×10⁻⁶/K and 6.0×10⁻⁶/K, a transmission τ at λ≦254 nm of ≦0.1% (for a specimen thickness of 0.2 mm).
 10. The use o the glass as claimed in claim 9 for the production of fluorescent lamps.
 11. The use of the glass as claimed in claim 9 for the production of miniaturized fluorescent lamps.
 12. A fluorescent lamp produced from the glass as claimed in claim
 9. 13. A miniaturized fluorescent lamp as set forth in claim
 12. 